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Patented May 19, 1942 hire SULPHONATED ORGANIC COMPOUNDS CAPILLARY-ACTIVE MEDIA Wini'rid Hentrich, Duesseldorfi-Reishola, Carl Albert Lalnau, Duesseldorl, and Wilhelm Jakob Kaiser, Duesseldorf-Benrath, Germany, as-

V signors, by mesne assignments, to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Application August 29, 1935, Serial No. 38,438. In Germany August 29, 1934 24 Claims. (onto-457) This invention relates to certain sulphonated organic compounds having high capillary activity suitable per se and also in combination with other substances for many purposes in the arts wherever soap or soap-like substances are employed.

These compounds and their mixtures with other substances as herein described are excellently suitable as wetting, emulsifying, dispersing, foaming, washing, cleansing, penetrating and bleaching agents.

An object of the present invention is to produce agents of the above mentioned type which besides possessing improved capillary-active properties also possess greaterstabillty durin storage than similar agents possessing fatty acid radicals. Other objects and advantages will become apparent particularly upon consideration of the examples and embodiments of the invention hereinafter set out.

The sulphonated organic compounds oi the present invention may be referred to collectively as the sulphonation products of organic compounds containing at least 12 carbon atoms, at least 2 carbon rings and not more than one free cyclic bound hydroxyl group. These rings are wholly hydrogenated or partially hydrogenated to any degree. v

For forming the above described compounds, any number of substances may be employed including, tor example, any completely or partially hydrogenated aromatic or aliphatic-armmatic compounds which contain two or more carbon rings and only one free hydroxyl group joined to said rings. The carbon rings may be wholly separate within the molecule or may be directly bound together as in condensed nuclei. As starting materials suitable for the production of the compounds of the present invention there may be employed hydrogenated phenol com pounds, hydrogenated c: and B hydroxy-naphthyl compounds or compounds derived from anthra= cene or phenanthrene. Other hydrogenated car= bon rings may be contained in the compounds, such, for example, as hydrogenated 'phenyl-, toly1-, ethylphenyl-, propylphenyl-, butylphenyl-, isobutyl henyl-, heptylphenyl-, octylphenylcy= clohexylphenyl-, naphthyl, propylnaphthyl, bu= tylnaphthyl-, heptylnaphthyl-, octylnaphthyl radicals, and the like. Furthermore, the corresponding partially or completely hydrogenated derivatives of anthracene and phenanthrene may be employed, in the latter case the resin alcohols obtainable by reduction of colophony being suitable.

directly or over their atomic bridges, particularly those containing lower aliphatic carbon chains having from about 1 to 4 carbon atoms such as are represented by the formulas CH-,-, -CH=,CH'. -CH2CHaCHa-. Also carbon bridges which are branched may be employed as in the following formulas:

For certain purposes there may be used with especially valuable results the fully or partially hydrogenated derivatives of diand triaryl methanes, and as well such derivatives of diarylenes containing only one free hydroxy group, for example, of diphenyl, its homologues and substitution products. Furthermore benzol derivatives may be used and as well the corresponding deriva'tives oi naphthalene, anthracene and phe= nanthrene, and the like.

so The present invention extends furthermore to the presence of any number of other types oi radicals and groups within the molecule such as ether groups and ketone groups.

Capillary-active media of unusual value may 85 be obtained by hydrogenation, sulphonation and neutralization of the compounds possessing the following formulas:

p-benzylpbenol alpha-benzyi-beta-naphtbol The present invention is not limited to these The carbon rings may be bound to each other as mpo n s containing nly two carbon rings, but

extends also to those containing three rings. As an example of such compounds there may be mentioned derivatives of (4-oxyphenyD-diphenyl-methane of the formula:

The hydrogenation step may be accomplished by conventional methods. The hydrogenated products may be obtained satisfactorily by heating the aromatic or other unsaturated cyclic compound at elevated temperatures and under superatmospherlc pressure in the presence of catalysts of the nature of nickel, copper, cobalt,

chromium, the noble metals, or catalysts composed of combinations of these metals. Catalysts of the nature of molybdenum and tungsten, and other similar substances, are insensitive to the sulphur content of the material treated. The hydrogenation is efiected in such manner that the hydroxyl group or groups of the aromatic radicals are retained and the aromatic radical either wholly or partially converted into hydro-aromatic radicals. During the hydrogenation any oxygen atoms and sometimes also other atoms present in the molecule may be eliminated by the reduction if the same is necessary as is the case when aromatic hydroxyl compounds of the formula Ar.CO.Ar'.Ol-I (Ar and Ar equal aromatic radicals) are employed. The adaptation of the above mentioned hydrogenation process is more clearly brought out in the examples to be hereinafter set out.

In order to obtain the sulphonation products of the hereinbefore described starting materials, it is suitable to employ any of the conventional sulphonation agents including concentrated sulphuric acid, fuming sulphuric acid, sulphur trioxide, chlorosulphonic acid and addition products of sulphur trioxide upon tertiary bases, for example, pyridine, and the like. In certain sulphonation reactions, it is advantageous to employ also a dehydrating agent or catalyst such as acetic anhydride or other organic or inorganic compound having an afllnity for water. Furthermore, the sulphonation may be aided by the presence of solvents or diluents of the nature of the lower alkyl or higher alkyl ethers. In order to cause the reaction to proceed in the desired manner, the temperature may be regulated from points below 0C. up to boiling or above. The nature of the sulphonation product obtained depends upon all of the reaction conditions employed. It is possible to obtain true sulphonic acids, or sulphuric acid esters, or mixtures of the same in any proportions. The esters are better for some purposes and the sulphonates for others.

Although the sulphonation products may be applied as such for many purposes, itis preferred that they be used in the form of their neutralization products. Among the water soluble salts suitable are the sodium salts, potassium salts, ammonium salts and the soluble salts of organic bases, such as, for example, of triethanolamine and of aminopropandiol.

The acid sulphonation products and their salts, as above described, of the wholly or partially hydrogenated organic compounds containing at least 12 carbon atoms, at least 2 carbon rings and only one free cyclic bound hydroxyl group, may be very eflectively employed alone in a large number of commercial processes, but they may be used with considerable advantage while in mixture with certain other substances. They can be employed in neutral, acid and alkaline liquids and baths, and especially in baths containing electrolytes. In a number of processes capillary-active agents may be used to advantage with substances adapted to impart alkalinity to aqueous solutions of the agent. Alkaline substances of various types may be used including the alkaline salts of the nature of the alkali carbonates, for example, soda and trisodium phosphate or other alkali metal orthophosphates, pyrophosphates, metaphosphates, polyphosphates and subphosphates, for example,

vtetrasodium pyrophosphate, sodium hexametaphosphate, sodiumpolyphosphate (NasPiOia), and sodium subphosphate. Other alkaline agents include water glass, sodium metasilicate, and as well, other metasilicates and the alkali metal borates such as borax.

In addition to the alkalinity imparting agents, there may be used to advantage in many cases certain neutral agents of the nature of sodium sulphate or the alkali metal salts of the higher molecular organic acids, for example, the sodium salt'of naphthalene sulphoacid.

The capillary-active media herein described may be employed to advantage particularly where some bleaching action is required, with oxygenyielding per compounds, for example, the peroxides such as sodium peroxide and per salts like the perborates, persulphates, percarbonates, perphosphates, perpyrophosphates, which are used preferably in the form of their alkali metal salts. especially the sodium salts. In order to impart additional beneficial properties, there may be added other substances possessing, wetting, foaming, emulsifying, dispersing, washing, cleansing, softening, rinsing, penetrating, or other similar properties. There may be used in particular ordinary sodium soaps or potassium soaps. However, other wetting agents which are stable to lime, for example, the sodium salt or oleylmethyl taurine may be used.

In order to impart special properties to the herein described capillary active media, there may be added thereto any one of a number of organic solvents of the nature of the hydrocarbons, for example benzine, benzol, or the alcohols including both those of low molecular weight, such as ethyl, propyl and butyl alcohol, and those of high molecular weight like lauryl alcohol, benzyl alcohol, cyclohexanol, cyclohexanone, and the like. There may also be added thereto compounds of the nature of superfatting agents, for example, wool fat or enzymes like ureases or pancreatin. If a disinfecting action is desired in the product, such may be imparted thereto by the addition of phenol compounds, for example. parachlorometacresol. The capillary-active media may also be used together with other ingre dients adapted to impart other types of cleansing and scouring properties such as by the use of abrasives of the nature of sand.

The above described mixtures may be prepared according to conventional methods in stirring equipment of any kind, in ball mills Or in other similar mixing apparatus. It is sometimes of advantage to mix the materials by atomization of one or more of the liquid or dissolved substances. The mixtures may be sold in the market as such, or the individual constituents thereof may be separately marketed and mixed at the place of the like.

use. Where the mixtures are to be dissolved in liquids their constituents may be separately dissolved and the solutions mixed, or the dry mixture of all of the ingredients may be simultaneously dissolved.

The herein described compositions containing a proportion of the capillary-active substances may be sold in the market in a solid form such as in the form of powder, flakes, granules. strips or other shapes. These particular forms are especially adapted for products to be sold for use in the household. It is desirable in many cases, particularly in the trades, for marketing the compositions in the form of solutions in which the composition may be completely dissolved or emulsified. Where the compositions are intended for cosmetic preparations, polishing agents, soap,

creams, and the like, it is advantageous to market the same in the form of pastes or creams. Example 1 Two hundred parts by weight of cyclohexyl phenol, in the presence of a nickel catalyzer, are

hydrogenated with 40 atmospheres hydrogen pressure at approximately 200 C. After absorption of 3 moles of hydrogen,'the hydrogenated product is filtered off from the catalyzer while being heated and is then distilled off under reduced pressure. Next, the mass is sulphonated in ethereal solution by means of chlorosulphonic acid while being stirred well and during cooling. By neutralization with soda lye, the sodium salt of the sulphuric acid ester of cyclohexyl-cyclohexanol is obtained. This compound when mixed with warm water from the faucet yields excellent foaming and wetting solutions.

An isomeric product is obtained if cyclohexylidencyclohexanone is used as a starting material. By hydrogenation in the presence of a nickel catalyst with 100 atmospheres hydrogen at 180 C. this substance yields a product which boils at 154-l56 C. under 12 mm. pressure and which shows a hydroxyl number of 290. This substance is sulphonated and neutralized as described above. Aqueous solutions of the sodium salt of the sulphuric acid ester of the cyclohexyl-cyclohexanol possess capillary-active properties,

These products are suitable for use in all processes where the presence of capillary-active substances are desired. Among the many uses, there may be mentioned especially their employment in connection with dyeing processes. The substances can be used for wetting-out and for stirring into pastes the powdered dyestuffs which are to be converted into aqueous liquids, Furthermore, they simplify the preparation of pastes and is especially of advantage. For after-soaping of dyeings andprintings, which are produced on the fiber by development of water insoluble azo dyes, the soap can be completely or partially substituted by the sulphonation-products here mentioned, or their salts.

Instead of cyclohexyl phenol, there may be used also cyclohexyl cresols or mixtures of the various cyclohexyl cresols, which by addition of a catalyst can be obtained from cresol or a mixture of the different cresols and cyclohexyl chloride or cyclohexene, said last mentioned substance being obtainable from cyclohexanol by treatment with dehydrating agents, as, for example, P205. These substances can be used as starting substances and can be converted into valuable capillary-active media. by following the procedure of the example.

In vat dyeing, also, their application The cyclohexyl radical, which represents one component of the substances mentioned, may carry other and additional substituents, as, for example, methyl-, ethyl-, propyl-, isopropyl-, butyl-, and isobutyl radicals or any number or mixture of these radicals, for instance both the methyl radical and the isobutyl radical.

Valuable capillary-active media in accordance with the invention can be obtained in the following manner: Cyclic ketones of the nature of cyclohexanone may be reacted by heating with alkaline condensation agents, for example,'an alcoholic solution of potassium hydroxide, and converted into resinous condensation products. By reduction of such products, substances are ob tained, which on the one hand possess more than 12 carbon atoms ad more than 2 carbon rings and on the other hand one free cyclic bound hydroxyl group. These products can be sulphonated and neutralized as described above.

' Example 2 Two hundred and ten parts by weight of dicyclohexyl phenol arehydrogenated in the presence of a nickel-containing mixed catalyst at with a dilute solution of sodium hydroxide, the

solid reaction product is filtered with the aid of suction and then dried. Aqueous solutions of the resulting sodium salt of the sulphonation product of dicyclohexylcyclohexanol possess unusually good foaming and moistening properties.

Products of this nature are suitable for many different types of processes employed in the textile industry. They can be used in bleaching baths for the treatment of cotton, which baths contain in addition substances which react alkaline in solution and also hydrogen peroxide. They also can be employed for the sizing of artificial silk in which case they are used in combination with gum arabic and glycerine. By adding a small quantity of the substances to the proper acid solutions, the process of fulling wool may be accelerated. By this treatment the feel of the goods becomes more open, softer and fuller than when the acid alone is used. Because of the unusual emulsification power of the sulphon- Example 3 One hundred and eighteen parts by weight of parabenzyl phenol and 12 parts by weight of a nickel catalyst are introduced'into an autoclave provided with an agitating means. The contents of the autoclave are then-heated to a temperature of 150 to 200 C. under a hydrogen pressure of 150 atmospheres. After about two hours treatment 6 moles of hydrogen will be absorbed.

he resulting product is then dissolved in ether and then filtered to remove the nickel from the solution. The solution is then washed with soda lye and subsequently washed with water after which it is dried over sodium sulphate. The ether is then distilled off after which the residue is distilled with the aid of a vacuum. The resulting mass is a viscous, colorless oil of a boiling pointiz of 155 to 165 C. One hundred and ninety-six parts by weight of the product thus obtained are dissolved in 500 parts by weight of ether and while the solution is being cooled, sulphonation is effected by slowly adding an ethereal solution of 116 parts by weight of chlorosulphonic acid. The product is then neutralized with sodium hydroxide and heated to distill oil the ether after which the mass is heated to boiling in the presence of alcohol. When this alcohol solution is permitted to cool, the sodium salt of the sulphonation product separates out in the form of crystals. When these crystals are dissolved in water, they yield excellent foaming and moistening solutions which can be advantageously used for the treatment of textiles and as well as a substitute for soap.

Products having very similar properties and useful for the same purposes can be prepared by using instead of the sodiumsalt, other salts such as, for example, the potassium salt, the ammonium salt, the triethanol amine salt, the aminopropandiol salt, and other like organic salts.

The benzyl phenol used in this example may be manufactured in known manner frombenzyl chloride and phenol in the presence of zinc. In the place of benzyl chloride there may be substituted various substituted benzyl chlorides including, for example, the methyl-, ethyl-, propyl-, isopropyl-, butyl-, or isobutyl'benzyl chloride, or, if desired, bencyl chlorides which in their nucleus are substituted by several alkyl radicals of from 1-5 or more carbon atoms.

In the production of compositions of the present invention, the above mentioned sodium salts of the sulphonation products can advantageously be combined with alkaline-yielding inorganic salts as, for example, soda, trisodium phosphate, sodium pyrophosphate, sodium hexametaphosphate, sodium polyphosphate (Na6P4013) water glass, sodium metasilicate or borax. The compositions thus produced possess good cleansing and rinsing powers.

Example 4 Benzylcresol is hydrogenated in an autoclave provided with stirring apparatus at approximately 200 C. in the presence of a nickel catalyst, under a hydrogen pressure of approximately 100 atmospheres. When sufiicient hydrogen is absorbed to saturate 6 double bonds, the product is separated from the catalyst and subjected to distillation. The perhydro benzyl cresol obtained boils at from 2-3 mm. of pressure at 140 to 150 C. A solution of 210 parts by'weight of this product is formed by adding an equal quantity of an organic solvent such as ether. While this solution is being substantially cooled, there is slowly added thereto 122 parts by weight of chlorosulphonic acid. By neutralization with sodium hydroxide, the sodium salt of the sulphonation product is obtained as a white powder.

The resulting product possesses excellent capillary activity and is particularly suited for use in pharmaceutical preparations, in connection with metal treatment, for the preparation of agents for combating parasites and for use in dust binding agents. It is also suitable for use in the textile industry and for the treatment of the raw materials used in the ceramic industry. It is of use for the production of protective colloids and for the acceleration of saponiflcation. In the leather industry, the addition of the herein described sulphonation products has a favorable effect upon the treatment liquids during the manufacture and as well during the finishing treatment, in which case the action of the treatment liquids is considerably accelerated and increased. Thesubstances also impart softness and pliability to various refining processes used in the treatment of fibrous materials.

The benzyl cresol can be obtained by an suitable method, .but is preferably obtaine in a known manner by the action of benzyl chloride upon cresol in the presence of zinc. The benzyl chloride may possess one or several substituent groups described in Example 3. Similar compounds are obtainable if substances of the nature of C-benzoyl ortho-cresol, C-phenylacetyl orthocresol, beta-phenyl propionyl orthocresol of the formula:

C Ha

which likewise are obtainable simply by suitable condensation are reduced, sulphonated and neutralized as described above. Even if the gammaphenyl proDyl orthocresol is converted in the manner. described, substances are obtained which contain 2 carbon rings which are thus combined with each other .by a short aliphatic chain of the nature hereinbefore described.

Example 5 hydroxyl group may be derived from cresol in stead of from phenol. Products containing 3 hexarings are present when dibenzyl phenol and similar products are used as starting substances, which substances may be obtained by condensation of 2 moles of,benzyl chloride with one mole of phenol.

Exampie 6 Tetrahydronaphthalene after cooling is treated by introducing purified chlorine during exposure to direct sunlight or to the action of suitable artificial light. By introducing the-chlorine into thev tetrahydronaphthalene, the latter is always present in excess, thereby facilitating the reaction. The chlorated compound obtained is then condensed with phenol or cresol, the best results being obtained when an excess of phenol is used. The resulting compound is then hydroaaeacsv is excellently suitable as a capillary-active agent.

Substances of, similar constitution can also be obtained if instead of tetrahydronaphthalene there is used decahydronaphthalene. By the action of chlorine uponsuch compound, a mixture of monoand dichlorodecahydronaphthalene is obtained. In order to obtain these products in pure form they may be separated by fractional distillation. By condensing the monochloride product with cresol there is obtained decahydronaphthylcresol. When the dichloride product is condensed only one chlorine atom is separated of! as hydrogen chloride by reaction with the cresol, while the other chlorine atom reacts with a hydrogen atom of the ring thereby separating off hydrogen chloride thus leading to the formation of a double bond; by this procedure octohydronaphthylcresol is obtained. Instead of following this procedure for obtaining the substances to be used according to the present invention, it is permissible to start directly from a mixture of the two chlorine compounds and then to condense them by treatment with cresol.

Compounds containing a naphthalene ring may be condensed with cresol by starting with an octahydronaphthalene which, for example, may be obtained from perhydro-beta-naphthol by treatment with dehydrating agents of the nature of phosphorpentoxide or zinc chloride. By using the cresol in excess, decahydronaphthyl cresol is obtained in an excellent yield.

Fifteen hundred parts by weight of decahydronaphthyl orthocresol obtainable from chlorodecahydronaphthalene by condensation with orthocresol are hydrogenated in the presence of a nickel catalyst under 40 atmospheres hydrogen from menaphthyl chloride, i. e.. alpha-naphthyl methyl chloride and phenol are hydrogenated by treatment-in an autoclave provided with a stirring apparatus by using a nickel catalyst at a temperature approximating 200'. C. under a pressure of about 100 atmospheres of hydrogen.

As soon as an amount of hydrogen is absorbed which corresponds to that required to saturate 8 double bonds. the product is separated from the catalyst and subjected to distillation The perhydromenaphthyl phenol boils at 190-210 C. un-

der 0. pressure of 13 mm. and is colorless and highly viscous at room temperature. One hundred parts by weight of this product are dissolved ir 400 parts by weight of ether, which mass during cooling is then subjected to treatment with 47 parts by weight of chlorosulphonic acid. After neutralization with sodium bicarbonate and drying the sodium salt of the sulphonation product is obtained as a colorless powder. Aqueous solutions of this product possess a good foaming and moistening capacity and therefore can be used to advantage as washing, cleansing, emulsification, dispersion, foaming and penetration agents.

' the method of Example 7, or instead at the lower pressure at a temperature of approximately 200 C. After 3 molecules of hydrogen are absorbed the hot mass is filtered from the catalyst and the resulting solution distilled at 14 mm. pressure between 203 and 210 C. The hydrogenated product obtained comprises a transparent oil which is quite viscous at ordinary temperatures. Three hundred parts of this oil are dissolved in ether and then sulphonated by adding slowly 170 parts by weight of chlorosulphonic acid while the mass is being stirred and cooled. After neutralization with sodium hydroxide and separation of the organic solvent, the sodium salt of the sulphuric acid ester is obtained as a colorless powder by atomizing an aqueous solution of the same at a temperature of 110 C. The resulting product forms solutions even when hard water is used which possess strong capillary activity and good foaming and wetting capacity.

Compositions within the scope of the present invention may be obtained by combining such products with per-compounds of the nature of sodium perborate, sodium persulphate, potassium percarbonate, sodium perphosphate,.sodium perpyrophosphate and peroxides like sodium superoxide, the properties of which solutions may be increased by the addition of suitable stabilization agents or by the addition, if necessary, of alkaline reacting inorganic salts such as soda, trisodium phosphate and other phosphates like sodium pyrophosphate. By this procedure good detergents and rinsing agents suitable particularly for the washing and rinsing of textiles are obtained.

Example 7 Two hundred and thirty-four parts by weight of menaphthyl phenol which can be obtained hydrogen pressure of say 40 atmospheres. Said product is then hydrogenated to produce the perhydromenaphthyl cresol, which at a pressure of 2 mm. boils at 190 to 200 C. and at 20 C. is a colorless clear resin. Suitable sulphonation products thereof can be obtained through the use of the sulphonation procedure outlined in Example 4. The sodium salt of the sulphonation products is a colorless powder which dissolves to form a clear solution in water of a hardness as high as 12. Its solutions have high foaming-and moistening capacities. Similar products may also be obtained by the use of hydrogenated naphthol orthocresol. Here also, it is possible to introduce substituents into the nucleus to produce substances of the nature of isobutyl naphthoyl'cresol, and the resulting compounds are suitable as starting materials for producing the compounds of the present invention.

Additional valuable products may be obtained by starting with menaphthyl cresol which has not been completely hydrogenated. By proper selection of sulphonation procedure; products diflering to a considerable extent may also be obtained. Valuable capillary-active media, for example, may be obtained by the following process. Twenty parts by weight of an incompletely hydrogenated menaphthyl orthocresol are gradually introduced during stirring into parts by weight of liquid sulphur dioxide at a. temperature of -15 C. To this solution 10.2 parts by weight of chlo'rosulphonic acid are added in a continuous stream. Although it is permissible for the temperature to increase a few degrees during this step a too greatincrease should be avoided by cooling the mass. After all of the chlorosulphonic acid has been added. the mass is stirred for about one and one-half hours at a temperature of approximately -10 0., after which the sulphur dioxide is carefully evaporated oil. The residue is then mixed with asmall quantity of ether and neutralized at a temperature of heated gases. There may be mentioned in this connection another sulphonation agent obtainable by compounding pyridine with chlorosulphonic acid at a temperature of from to 35 C.

In the foregoing process the naphthalene derivatives may be replaced by the corresponding anthracene and phenanthrene derivatives. These derivatives are obtainable substantially by the same method inasmuch as anthracene and phenanthrene, or their derivatives, may be treated with i'ormaldehydeand hydrochloric acid to introduce the -'CHzCl group. and the chlorine containing compounds thus produced upon escape of the hydrogen chloride being condensible with phenol, cresols andthe like, after which they are hydrogenated, sulphonated and neutralized as described above. Phenanthrene derivatives are easily obtainable in a simple manner inasmuch as the abietic acid contained in colophony is suitable for an initial material and may be treated by subjecting the same to a catalytic high pressure hydrogenation, or by a reduction according to Bouveault and Blanc. The

hydroxyl group of this compound can, for example, be substituted by a chlorine atom by means of a treatment with thionyl chloride. The resulting chloride can be condensed with phenol,.

cresols and the like by following the procedure hereinbefore described. The process may be very advantageously carried out by reacting the resin alcohol directly with the phenol mentioned by employing a suitable condensation agent. The suli'onation and neutralization steps may be eifected also in the manner above disclosed. Here also, the phenol or cresol radical may possess substituents of a most varied nature. For example, alkyl radicals like methyl, ethyl. propyl, isopropyl, butyl and isobutyl radicals.

Valuable products can also-be obtained from condensation products of naphthene alcohols or the corresponding chlorides with phenol or cresols. The sulphonation products of all the compounds mentioned above and their salts constitute valuable capillary-active media which are suitable for use in the most varied processes of industry, for they moisten. foam and disperse with considerable power. They may be used successfully in the textile industry, for example, for steeping, wetting, bleaching and as a finishing agent. for washing raw wool, for use in various dyeing processes, for dyeing wool in acid baths, for levelling, as an assistant in printing processes in connection with cloth printing and furthermore. as an assistant in industries wherein caoutchoue is worked up; also for pharmaceutical purposes, in connection with metal works, for the preparation of agents for combating parasites,

and as agents for dust binding and for use in the ceramic industry and in foam producing fire extinguishers.

Example 9 The products described in" the foregoing examples can also be obtained through the use of commercial mixtures of cresols which comprise mixtures of the different isomeric cresols with phenols and other substances. Thus a condensation of menaphthyl chloride and commercial cresol which contains besides menaphthyl cresol also 25% of higher condensation products, can be completely hydrogenated according to the method described in Example 4, after which it is sulphonated by any suitable method. The sodium salt of the sulphonation product is obtained in the'form of a light almost colorless powder.

Here also, the homologues and analogues of menaphthyl chloride can be used, for example,

Example 10 The products obtained by condensation of one mole of phenol with 2 moles of a chlorine-containing aromatic-compound may also be used as starting materials. For example, 2 moles of menaphthyl chloride and one mole of ortho-.

cresol are condensed and the reaction product is completely or partially hydrogenated, sulphonated and then neutralized in the manner hereinbefore described. By such procedure, valuable capillary-active substances are obtained which can be employed to advantage in combination with ordinary soaps and soap-containing cleansing agents. Particularly good products may be I obtained by combining the compositions with known capillary active substances which are stable to lime.

Example 11 Starting materials may be employed wherein the hydroxyl group is joined upon a naphthalene, anthracene or phenonthrene ring. The substances heretofore described in the preceding examples possess the hydroxyl group upon a benzol ring. Valuable capillary active agents may be obtained from the hydroxy condensed -nuclei compounds by the following procedure. One hundred and seventeen parts by weight of alphabenzyl beta-naphthol are heated in an autoclave provided with a stirring device to a temperature of 200 C. in the presence of a nickel catalyst under a hydrogen pressure up to 200 atmospheres of hydrogen. When absorption of hydrogen ceases. the product has taken up 8 moles. This product is then sulphonated with four times the quantity of concentrated sulphuric acid. After neutralization, the sodium salt of the sulphonation product .of perhydrobenzyl naphthal is obtained which yields strong foaming and good moistening aqueous solutions excellently adapted for the treatment of textiles and as a substitute for soap. Analogous compounds may be obtained by the use of beta-phenyl acetyl naphthols as the starting materials. There also may be mentioned isopropyl benzoyl naphthols.

The sulphonates of the foregoing compounds may be combined with cleansing agents of various kinds. For example, sand or other abrasive and, if necessary, with other alkaline yielding inorganic salts like soda, trisodium phosphate, sodium Dyrophosphate, or sodium metaphosphate. The resulting compositions are valuable securing and cleansing agents.

Example 12 By completely hydrogenating benzyl alphanaphthol a clear highly viscous oil is obtained. One thousand parts by weight of this oil are ous natures.

sulphonated according to the method described in Example 4 and the resulting mass neutralized with sodium bicarbonate. The neutralized prodnot is then filtered by suction and purified by extraction with acetone. After evaporation ,of the acetone, the sodium salt of the sulphonation product is obtained as a light brown oil which when dissolved in water in a one-half percent solution possesses good capillary-active qualities even when the water is of 12 hardness.

Menaphthyl alpha-naphthol obtainable from menaphthyl chloride and naphthol by an analogous method is hydrogenated, sulphonated and neutralized to form an alkali metal salt, for example, the sodium or-potassium or ammonium salt.

Inasmuch as the above described starting materials possess several aromatic rings, they naturally can be easily partially hydrogenated as well as wholly hydrogenated. Compositions of the-present invention may be produced from the above mentioned sulphonated compounds which possess excellent detergent and cleansing power. Such may be formed by'adding alkaline reacting substances or instead neutral substances, as, for example, neutral reacting inorganic salts of the nature of sodium sulphate and magnesium sulphate or salts or organic acids as, for example, the sodium salt of naphthalene sulphoacid, or of isopropyl or isobutyl naphthalene sulphoacid.

The new capillary-active substances per se herein described may be used to advantage upon all occasions where capillary-active qualities of liquids, especially of aqueous solutions or emulsions are to be increased. In general, it may be stated that because of the capillary active qualities. the new agents may. be used in many industrial processes where there is need for foam production, emulsification, dispersion, wetting, impregnation, peptization, stabilization, levelling, distribution or for dissolving purposes, etc. Therefore, they may be used as soap substitutes for the manufacture of impregnation agents, agents for combatting parasites and the like. They may also be used as expedients in indushereindisclosed but that it includes all compounds equivalent to those disclosed and coming within the scope of the terms employed in the appended claims.

We claim:

1. A capillary-active compound, a sulphonation product of a saturated organic compound containing at least 12 carbon atoms, at least 2 carbon rings and one free hydroxyl group joined to one of said rings.

2. A capillary-active compound. a water soluble salt of a sulphonation product of a saturated organic compound containing at least 12 carbon atoms, at least 2 carbon rings and one free hydroxyl group joined to one of said rings.

3. A capillary-active compound, a sulphonation product of a completely hydrogenated cyclic organic compound containing at least 12 carbon atoms, at least 2 carbon rings and one tree hydroxyl group joined to one of said rings.

' 4. A capillary-active compound, a sulphona tion product of a saturated cyclic organic compound containing 12 carbon atoms, at least, 2 carbon rings and one free hydroxyl group joined to one of said rings.

5. A capillary-active compound, a su'lphona tion product of a completely hydrogenated aromatic organic compound containing at least- 12 carbon atoms, at least 2 carbon rings and one free hydroxyl group joined to one of said rings, the ring to which the free hydroxyl group is joined being a hydrogenated benzene ring.

6. A capillary-active compound, a sulphonation product of a completely hydrogenated aromatic organic compound containing at least 12 carbon atoms, at least 2 carbon rings and one free hydroxyl group joined to one of said rings, the ring to which the free hydroxyl group is Joined being a hydrogenated naphthalene ring.

7. A capillary-active compound, a sulphonation product of a completely hydrogenated aromatic organic compound containing at least 12 carbon atoms, at least 2 carbon rings andone tree hydroxyl group joined to one of said rings,

tries wherein rubber is to be worked up, also in the leather, iur'and especially the textile industry in connection with refining methods of vari- They can also be used in connection with washing and cleaning of textiles, clothes and other articles of commerce. Solutions prepared from the new agents may be used at warm or cold temperatures.

In contrast to the other comparable compounds which can be obtained by sulphonation of hydrogenated polynuclear organic compounds containing 2 or more hydroxyl groups, the substances prepared in accordance with the present disclosure possess a considerably increased foaming and wetting capacity and in addition are of considerable value because of their greater stability. In contrast with the known capillaryactive agents which contain a fat or fatty acid radical, the present products do not have a tendency to become rancid or to develop a disagreeable odor even after long storage. In the appended claims, it should be understood that the terms sulphonation product" or "sulphonation products" are intended to cover both the sulphuric acid esters and the true sulphonates. Furthermore, the claims are to be interpreted as including the water soluble salts of both esters and true sulphonates.

It should be understood that the present invention is not limited to the specific compounds a ring to which the free hydroxyl is not joined being a hydrogenated aryl ring.

8. The capillary-active compound described in claim '7 wherein the hydrogenated aryl ring is one of two mono-nuclear rings contained in the compound.

9. The capillary-active compound described in claim 7 wherein the hydrogenated aryl ring is of a condensed nucleus.

10. The capillary-active compound described in claim 7 wherein the hydrogenated aryl ring is of hydrogenated naphthalene.

11. The capillary-active compound described in claim 7 wherein the hydrogenated aryl ring is derived from a resin alcohol.

12. As capillary-active compounds for wetting, cleansing, emulsifying, etc., the compounds being sulphonation products of saturated polynuclear organic compounds containing at least 12 carbon atoms, at least 2 carbon rings and one free hydroxyl group joined to one of said rings, said rings being directly connected together.

13. As capillary-active compounds for wetting. cleansing, emulsifying, etc., the compounds bemg water soluble salts of sulphonation products of saturated polynuclear organic compounds containing at least 12 carbon atoms, at least 2 carbon rings and one free hydroxyl group joined 14. As capillary-active compounds for wetting,

cleansing, emulsifying, etc., the compounds being sulphonation products of saturated polynuclear organic compounds containing at least 12 carbon atoms, at least 2 carbon rings and one free hydroxyl group joined to one of said rings, said rings being connected together through a carbon bridge. I v

' 15. As capillary-active compounds for wetting, cleansing, emulsifying, etc., the compounds be: ing water soluble salts of sulphonation products of saturated Dolynuclear organic compounds containing at least 12 carbon atoms, at least 2 carbon rings and one free'hydroxyl group joined .to one of said rings, said rings being connected together through a carbon bridge.

16. The capillary-active compound described in claim 14 wherein the rings are connected together through an aliphatic radical of from 1 to 4 carbon atoms. p

17. A capillary-active compound, a sulphonation product of a completely hydrogenated aromatic organic compound containing at least 12 carbon atoms, at least 2 carbon rings and one free hydroxyl group Joined to one 01' said rings, there being at least one alkyl radical of from 1 to 5 carbon atoms Joined to 'a ring.

18. The process of preparing compounds having capillary active properties which comprises hydrogenating an organic compound containing at least 12 carbon atoms, at least 2 carbon rings and one free-hydroxyl group joined to one of said rings. and then sulphonating said hydrogenated compound.

19. The process of preparing capillary active compounds which comprises hydrogenating a diaryl compound containing one free hydroxyl group joined to one of said rings sulphonating the resulting hydrogenated compound and neutralizing to form a water soluble salt thereof.

20. The process which comprises hydrogenating a monohydroxy diaryl alkane and sulphonating the resulting hydrogenation product.

21. As new compounds, completely hydrogen- 23. Alkali metal salts of sulphates having the 7 general formula:

R-C--OSO3M6 in which R represents a cycloaliphatic hydrocarbon radical containing at least 6 carbon atoms, C stands for a cyclohexane nucleus, and Me represents an alkali metal.

24. sulphates having the general formula:

. R-CX in which R, represents a cycloaliphatic hydrocarbon radical of at least six carbon atoms, C represents a cycloaliphatic radicalyand X represents a sulphate group which is directly attached to a carbon atom in the 0 ring.

WINFRID HENTRICH. CARL ALBERT LAINAU. WILHELM JAKOB KAISER. 

